Stripping compositions for removing photoresists from semiconductor substrates

ABSTRACT

This disclosure relates to compositions containing 1) at least one water soluble polar aprotic organic solvent; 2) at least one quaternary ammonium hydroxide; 3) at least one compound comprising at least three hydroxyl groups; 4) at least one carboxylic acid; 5) at least one Group II metal cation; 6) at least one copper corrosion inhibitor selected from the group consisting of 6-substituted-2,4-diamino-1,3,5-triazines; and 7) water. The compositions can effectively strip positive or negative-tone resists or resist residues, and be non-corrosive to bumps and underlying metallization materials (such as SnAg, CuNiSn, CuCoCu, CoSn, Ni, Cu, Al, W, Sn, Co, and the like) on a semiconductor substrate.

CROSS-REFERENCE TO RELATED APPLICATION

The present application claims priority to U.S. Provisional ApplicationSer. No. 62/340,204, filed on May 23, 2016, which is hereby incorporatedby reference in their entirety.

FIELD OF THE DISCLOSURE

The present disclosure relates generally to novel stripping compositionsfor removal of photoresists (e.g., positive or negative photoresists) orphotoresist residues from semiconductor substrates. Specifically, thepresent disclosure relates to alkaline compositions useful for removingphotoresists or photoresist residues after an etching or plasma ashingprocess.

BACKGROUND OF THE DISCLOSURE

In the manufacture of integrated circuits, a flip chip process known asControlled Collapse Chip Connection (C4) process for interconnectingsemiconductor devices, such as IC chips and microelectromechanicalsystems (MEMS) to external circuitry with solder bumps that have beendeposited onto the chip pads, has now become quite well established.Thick negative-tone photoresist is commonly applied during flip chip orC4 processes and commercially available resist stripping formulationsfor thick negative-tone resist are predominantly DMSO(dimethylsulfoxide) or NMP (N-methylpyrrolidone) plus TMAH(tetramethylammonium hydroxide) based formulations. However, thosecommercially available resist stripping formulations for thicknegative-tone resist may exhibit the problems of insufficient resiststripping capability, short bath life, or poor compatibility with metalsubstrates and bump compositions. In addition, foaming issues producedby the dissolved photoresist or the surfactants in the dissolvedphotoresist can occur.

SUMMARY OF THE DISCLOSURE

This disclosure describes the development of resist strippingcompositions tailored for devices containing bumps and metallizationmaterials (such as SnAg, CuNiSn, CuCoCu, CoSn, Ni, Cu, Al, W, Sn, Co,and the like). The inventors discovered unexpectedly that the ability toeffectively strip thick positive or negative-tone resist and benon-corrosive to bumps and underlying metallization materials (such asSnAg, CuNiSn, CuCoCu, CoSn, Ni, Cu, Al, W, Sn, Co, and the like) can beachieved by using the compositions of the present disclosure. Indeed, ithas been discovered that the compositions of the disclosure areeffective in suppressing Cu and Al etching while maintaining excellentstripping and cleaning performance. In addition, the compositions ofthis disclosure exhibit broad material compatibility and can effectivelycontrol foaming issues during the stripping process.

In some embodiments, this disclosure features a photoresist strippingcomposition that includes

-   -   1) at least one water soluble polar aprotic organic solvent;    -   2) at least one quaternary ammonium hydroxide;    -   3) at least one compound comprising at least three hydroxyl        groups;    -   4) at least one carboxylic acid;    -   5) at least one Group II metal cation;    -   6) at least one copper corrosion inhibitor selected from the        group consisting of 6-substituted-2,4-diamino-1,3,5-triazines;        and    -   7) water.

In some embodiments, this disclosure concerns a photoresist strippingmethod that includes contacting a semiconductor substrate containing aphotoresist or a photoresist residue with a photoresist strippingcomposition of this disclosure to remove the photoresist or photoresistresidue. In some embodiments, the stripping method further includesforming a semiconductor device (e.g., an integrated circuit device suchas a semiconductor chip) from the semiconductor substrate obtained bythe method described above.

DETAILED DESCRIPTION OF THE DISCLOSURE Definitions

As defined herein, unless otherwise noted, all percentages expressedshould be understood to be percentages by weight to the total weight ofthe stripping composition. Unless otherwise noted, ambient temperatureis defined to be between about 16 and about 27 degrees Celsius (° C.).

As defined herein, a “water-soluble” substance (e.g., a water-solublealcohol, ketone, ester, ether, and the like) refers to a substancehaving a solubility of at least 5% by weight in water at 25° C.

As used herein, the term “polar aprotic solvent” refers to a solventthat lacks an acidic proton and has a relatively high dipole moment(e.g., at least 2.7).

As defined herein, a “Group II metal cation” refers to a cation of ametal in Group II of the Periodic Table.

Tautomerization is herein defined as the formal migration of a hydrogenatom or proton accompanied by a switch of a single and an adjacentdouble bond. The mention, description, or claim of triazole compoundsalso includes the tautomers of the triazole compounds due to the lowactivation energy for tautomerization in the triazole ring system.

As defined herein, the term “triazole” does not include annelatedtriazoles such as benzotriazole or naphthotriazole or their derivatives.Although the triazoles of this disclosure may have cyclic substituents,the substituents are attached to the ring at only one carbon.

In some embodiments, this disclosure concerns a photoresist strippingcomposition including

-   -   1) at least one water soluble polar aprotic organic solvent;    -   2) at least one quaternary ammonium hydroxide;    -   3) at least one compound comprising at least three hydroxyl        groups;    -   4) at least one carboxylic acid;    -   5) at least one Group II metal cation;    -   6) at least one copper corrosion inhibitor selected from the        group consisting of 6-substituted-2,4-diamino-1,3,5-triazines;        and    -   7) water.

In some embodiments, the stripping compositions of this disclosurecontain at least one water soluble polar aprotic organic solvent. Thewater soluble polar aprotic organic solvent can be one water solublesolvent or a mixture of water soluble solvents in any ratio. Examples ofsuch solvents suitable for use in the present disclosure include, butare not limited to, dimethyl sulfoxide, sulfolane, dimethylsulfone,N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone,gamma-butyrolactone, propylene carbonate, 1,3-dimethyl-2-imidazolidinoneand mixtures thereof. In some embodiments, the water soluble polaraprotic organic solvent is dimethyl sulfoxide, sulfolane,gamma-butyrolactone, or N-methylpyrrolidone.

In some embodiments, the compositions of this disclosure contain the atleast one water soluble polar aprotic organic solvent in an amount of atleast about 30% by weight (e.g., at least about 40% by weight, at leastabout 50% by weight or at least about 60% by weight) and/or at mostabout 90% by weight (e.g., at most about 85% by weight, at most about80% by weight or at most about 75% by weight).

Optionally, the stripping compositions of this disclosure contain atleast one alcohol solvent, such as a water soluble alcohol solvent.Classes of water soluble alcohol solvents include, but are not limitedto, alkane diols (including, but not limited to, alkylene glycols),glycols, alkoxyalcohols (including but not limited to glycolmonoethers), saturated aliphatic monohydric alcohols, unsaturatednon-aromatic monohydric alcohols, alcohols (e.g., low molecular weightalcohols) containing a ring structure, and mixtures thereof. Thestripping compositions can include one alcohol solvent or a mixture ofalcohol solvents in any ratio. In some embodiments, the compositions ofthe disclosure do not contain at least one alcohol solvent.

Examples of water soluble alkane diols include, but are not limited to,2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol,1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol,and alkylene glycols.

Examples of water soluble alkylene glycols include, but are not limitedto, ethylene glycol, propylene glycol, hexylene glycol, diethyleneglycol, dipropylene glycol, triethylene glycol, and tetraethyleneglycol.

Examples of water soluble alkoxyalcohols include, but are not limitedto, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol,1-methoxy-2-butanol, and water soluble glycol monoethers.

Examples of water soluble glycol monoethers include, but are not limitedto, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol mono n-propyl ether, ethylene glycol monoisopropylether, ethylene glycol mono n-butyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether, diethylene glycolmonobutylether, triethylene glycol monomethyl ether, triethylene glycolmonoethyl ether, triethylene glycol monobutyl ether,1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol,2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropyleneglycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyleneglycol mono-n-propyl ether, tripropylene glycol monoethyl ether,tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether,and diethylene glycol monobenzyl ether.

Examples of water soluble saturated aliphatic monohydric alcoholsinclude, but are not limited to, methanol, ethanol, n-propyl alcohol,isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butylalcohol, 2-pentanol, t-pentyl alcohol, and 1-hexanol.

Examples of water soluble unsaturated non-aromatic monohydric alcoholsinclude, but are not limited to, allyl alcohol, propargyl alcohol,2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

Examples of water soluble, low molecular weight alcohols containing aring structure include, but are not limited to, tetrahydrofurfurylalcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

In some embodiments, the water soluble alcohol solvents are,alkoxyalcohols, tetrahydrofurfuryl alcohol, and water solublealkanediols. In some embodiments, the water soluble alcohol solvents are3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol,water soluble glycol monoethers, water soluble alkylene glycols, andtetrahydrofurfuryl alcohol. In some embodiments, the water solublealcohol solvents are 3-methoxy-3-methyl-1-butanol, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, ethylene glycolmono n-butyl ether, propylene glycol, hexylene glycol, andtetrahydrofurfuryl alcohol.

In some embodiments, when the photoresist stripping method describedherein employs a heated photoresist stripping composition describedherein, the water soluble alcohols can have a boiling point above 110°C. for safety considerations.

In some embodiments, the stripping compositions of this disclosurecontain the at least one alcohol solvent in an amount of at least about5% by weight (e.g., at least about 7% by weight, at least about 10% byweight or at least about 12% by weight) and/or at most about 60% byweight (e.g., at most about 45% by weight, at most about 35% by weightor at most about 25% by weight).

In some embodiments, the stripping compositions of this disclosurecontain at least one quaternary ammonium hydroxide. In some embodiments,the preferred quaternary ammonium hydroxide is a compound represented bythe general formula [NR₁R₂R₃R₄]⁺OH, where R₁, R₂, R₃, and R₄ areindependently a linear, branched or cyclic alkyl group optionallysubstituted by hydroxy, a substituted or unsubstituted phenyl group, ora substituted or unsubstituted benzyl group (e.g., a benzyl groupsubstituted or unsubstituted on its phenyl group). Substituents on thephenyl group and on the phenyl group of the benzyl group may includehalogen, hydroxyl, alkoxy, or alkyl. In some embodiments, the quaternaryammonium hydroxide is a tetralkylammonium hydroxide. In someembodiments, the quaternary ammonium hydroxide is a tetralkanol ammoniumhydroxide. In some embodiments, the quaternary ammonium hydroxide is amixture of two or more quaternary ammonium hydroxides in any ratio.

In some embodiments, the preferred quaternary ammonium hydroxide is acompound of the general formula [NR₁R₂R₃R₄]⁺OH, where R₁, R₂, R₃, and R₄are independently a C₁-C₄ alkyl group, a hydroxyethyl group, a phenylgroup, or a benzyl group.

Examples of suitable quaternary ammonium hydroxide compounds include,but are not limited to, tetramethylammonium hydroxide (TMAH),tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide,tetrabutylammonium hydroxide (TBAH), ethyltrimethylammonium hydroxide,diethyldimethylammonium hydroxide, methyltripropylammonium hydroxide,butyltrimethylammonium hydroxide, methyltributylammonium hydroxide,pentyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammoniumhydroxide (choline), (2-hydroxyethyl)triethylammonium hydroxide,(2-hydroxyethyl)triethyl-ammonium hydroxide,(3-hydroxypropyll)triethylammonium hydroxide,tris-2-hydroxyethylammonium hydroxide, tetraethanolammonium hydroxide,phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide andmixtures thereof.

In some embodiments, the quaternary ammonium hydroxide istetramethylammonium hydroxide, (2-hydroxyethyl)trimethylammoniumhydroxide (choline), benzyltrimethylammonium hydroxide,tetrabutylammonium hydroxide, or tetraethanolammonium hydroxide.

In some embodiments, the quaternary ammonium hydroxide is TMAH, TEAH,TBAH, choline, or tetraethanolammonium hydroxide.

In some embodiments, the stripping compositions of this disclosurecontain the at least one quaternary ammonium hydroxide in an amount ofat least about 0.1% by weight (e.g., at least about 0.5% by weight, atleast about 1% by weight or at least about 1.5% by weight) and/or atmost about 10% by weight (e.g., at most about 8% by weight, at mostabout 5% by weight or at most about 3% by weight).

In some embodiments, the stripping compositions of the disclosureinclude at least one Group II metal cation. Examples of suitable GroupII metal cations include Ca²⁺, Mg²⁺, Sr²⁺, and Ba²⁺. In someembodiments, the stripping compositions described herein can include theGroup II metal cation in an amount of at least about 5 ppm (e.g., atleast about 7 ppm, at least about 8 ppm, or at least about 10 ppm)and/or at most about 40 ppm (e.g., at most about 35 ppm, at most about25 ppm, at most about 20 ppm, or at most about 15 ppm).

Without wishing to be bound by theory, it is believed that a strippingcomposition containing solubilized Group II metal cations (e.g., calciumcation) can significantly reduce the Al etch rate of the strippingcomposition, thereby allowing the stripping composition to inhibit Aletch during use. Further, without wishing to be bound by theory, it isbelieved that, as Group II metal compounds are generally not verysoluble in the stripping compositions described herein, adding an agentthat can solubilize Group II metal cations (e.g., by forming a complexwith a Group II metal cation) can significantly increase the amount ofthe solubilized Group II metal cations in the stripping compositions,thereby improving their Al etch inhibition abilities.

Thus, in some embodiments, the stripping compositions of the disclosurecan include one or more compounds that improve the solubility of GroupII metal cations in water soluble polar aprotic organic solvents. Thesecompounds include compounds having at least three hydroxyl groups. Insome embodiments, the compounds are sugar alcohols. Sugar alcoholscontemplated for use in the compositions of the disclosure include, butare not limited to, glycerol, sorbitol, mannitol, erythritol, arabitol,isomalt, lactitol, maltitol, xylitol, threitol, ribitol, galactitol,iditol, and inositol. In some embodiments, the sugar alcohol is glycerolor sorbitol.

In some embodiments, the stripping compositions described herein caninclude at least at least one compound having at least three hydroxylgroups in an amount of about 0.1% by weight (e.g., at least about 0.5%by weight, at least about 1% by weight or at least about 1.5% by weight)and/or at most about 10% by weight (e.g., at most about 8% by weight, atmost about 5% by weight or at most about 3% by weight).

In some embodiments, the stripping compositions of the disclosure canalso include at least one carboxylic acid. Without wishing to be boundby theory, it is believed that carboxylic acids act in concert withcompounds having at least three hydroxyl groups can improve thesolubility of Group II metal cations in water soluble polar aproticorganic solvents. In some embodiments, examples of the at least onecarboxylic acid contemplated for use in the compositions of thedisclosure include, but are not limited to, monocarboxylic acids,bicarboxylic acids, tricarboxylic acids, α-hydroxyacids andβ-hydroxyacids of monocarboxylic acids, α-hydroxyacids or β-hydroxyacidsof bicarboxylic acids, or α-hydroxyacids and β-hydroxyacids oftricarboxylic acids. In some embodiments, the at least one carboxylicacid includes citric acid, maleic acid, fumaric acid, lactic acid,glycolic acid, oxalic acid, tartaric acid, succinic acid, or benzoicacid. In some embodiments, the carboxylic acid is citric acid.

In some embodiments, the stripping compositions described herein caninclude the at least one carboxylic acid in an amount of at least about0.1% by weight (e.g., at least about 0.2% by weight, at least about 0.3%by weight or at least about 0.4% by weight) and/or at most about 1.5% byweight (e.g., at most about 1.2% by weight, at most about 0.9% by weightor at most about 0.6% by weight).

The stripping compositions of the present disclosure generally containwater. In some embodiments, the water is de-ionized and ultra-pure,contains no organic contaminants and has a minimum resistivity of about4 to about 17 mega Ohms. In some embodiments, the resistivity of thewater is at least 17 mega Ohms.

In some embodiments, the stripping compositions of this disclosurecontain water in an amount of at least about 2.5% by weight (e.g., atleast about 5% by weight, at least about 7% by weight or at least about10% by weight) and/or at most about 25% by weight (e.g., at most about20% by weight, at most about 15% by weight or at most about 12.5% byweight).

In some embodiments, the stripping compositions of the presentdisclosure include at least one copper corrosion inhibitor, which is a6-substituted-2,4-diamino-1,3,5-triazine. The substituent on the2,4-diamino-1,3,5-triazine can be a linear or branched substituted orunsubstituted C₁-C₁₂ alkyl group (e.g., methyl, hexyl, —CH₂-aryl,CH₂OR¹⁰⁰, —CH₂SR¹⁰⁰, —CH₂(NR¹⁰⁰R¹⁰¹)), a substituted or unsubstitutedC₃-C₁₂ cycloalkyl group (e.g., cyclohexyl, methylcyclohexyl, orhydroxycyclohexyl), a substituted or unsubstituted aryl group (e.g.,phenyl, methoxyphenyl, or naphthyl), —SCH₂R¹⁰⁰, —N(R¹⁰⁰R¹⁰¹), or imidyl,where each of R¹⁰⁰ and R¹⁰¹, independently, is a linear or branched,substituted or unsubstituted C₁-C₁₂ alkyl group optionally containing anitrogen or oxygen atom in the alkyl chain, a substituted orunsubstituted C₃-C₁₂ cycloalkyl group optionally containing a nitrogenor oxygen atom in the cycloalkyl ring, a substituted or unsubstitutedaryl group, or R¹⁰⁰ and R¹⁰¹, together with the atom to which they areattached, form a ring. Substituents on the alkyl and cycloalkyl groupscan include, C₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxyl, and substituted orunsubstituted aryl. In some embodiments, substituents on the aryl groupsare electron donating (e.g., alkoxy) rather than electron withdrawing(e.g., halogen).

Examples of suitable 6-substituted-2,4-diamino-1,3,5-triazines include6-methyl-2,4-diamino-1,3,5-triazine;6-phenyl-2,4-diamino-1,3,5-dimethyltriazine; 1,3,5-triazine-2,4-diamine,6-[2-(2-furanyl)ethyl]-; 1,3,5-triazine-2,4-diamine,6-[(hexahydro-1-methylpyrrolo[3,4-c]pyrrol-2(1H)-yl)methyl]-;1,3,5-triazine-2,4-diamine, 6-[[(3-aminobutyl)thio]methyl]-;1,3,5-triazine-2,4-diamine, 6-(4,4-difluorocyclohexyl)-;1,3,5-triazine-2,4-diamine, 6-[(3-chlorophenyl)methyl]-;1,3,5-triazine-2,4-diamine, 6-[(phenylthio)methyl]-;1,3,5-triazine-2,4-diamine, 6-[(tetrahydro-2H-pyran-2-yl)methyl]-;2-(4,6-diamino-1,3,5-triazin-2-yl)-4-fluoro-phenol;1,3,5-triazine-2,4-diamine, 6-(1-ethylcyclopentyl)-;1,3,5-triazine-2,4-diamine,6-[[4-(diphenylmethyl)-1-piperazinyl]methyl]-; 9-acridinecarboxylicacid, 1,2,3,4-tetrahydro-4-[(4-methoxyphenyl) methylene]-,(4,6-diamino-1,3,5-triazin-2-yl)methyl ester;1H-Benz[de]isoquinoline-1,3(2H)-dione,2-[[(4,6-diamino-1,3,5-triazin-2-yl)amino]methyl]-; 9-acridinecarboxylicacid,2-(1,1-dimethylpropyl)-1,2,3,4-tetrahydro-,(4,6-diamino-1,3,5-triazin-2-yl)methylester; 1,3,5-triazine-2,4,6-triamine,N2-[2-[(7-chloro-4-quinolinyl)amino]ethyl]-; 1,3,5-triazine-2,4-diamine,6-[[4-(1-methylethyl)phenoxy]methyl]-; 1,3,5-triazine-2,4-diamine,6-[[3-(trifluoromethyl)phenoxy]methyl]-; 1,3,5-triazine-2,4-diamine,6-[[(tetrahydro-2H-pyran-2-yl)methyl]thio]-;N-cyclohexyl-2-[(4,6-diamino-1,3,5-triazin-2-yl)thio]-propanamide;3-chloro-4-[(4,6-diamino-1,3,5-triazin-2-yl)methoxy]-5-methoxy-benzonitrile;benzeneacetic acid, 3-methoxy-, (4,6-diamino-1,3,5-triazin-2-yl)methylester; 1,3,5-triazine-2,4-diamine, 6-[3-(1-pyrrolidinyl)phenyl]-;1,3,5-triazine-2-octanenitrile, 4,6-diamino-;s-triazine-2-butyronitrile, 4,6-diamino-; 1,3,5-triazine-2-propanoicacid, 4,6-diamino-; 1,3,5-triazine-2-methanethiol, 4,6-diamino-;benzamide, N-(4,6-diamino-1,3,5-triazin-2-yl)-4-hydroxy-; and1,3,5-triazine-2,4-diamine, 6-[(methylthio)methyl]-.

In some embodiments, the stripping compositions of this disclosurecontain at least one copper corrosion inhibitor in an amount of at leastabout 0.01% by weight (e.g., at least about 0.05% by weight, at leastabout 0.1% by weight or at least about 0.5% by weight) and/or at mostabout 10% by weight (e.g., at most about 7% by weight, at most about 5%by weight or at most about 2% by weight).

The stripping compositions of the present disclosure optionally includea defoaming surfactant. Examples of suitable defoaming surfactantsinclude polysiloxanes (e.g., polydimethylsiloxane), polyethylene glycolmethyl ether polymers, ethylene oxide/propylene oxide copolymers,tetramethyldecynediol, and glycidyl ether capped acetylenic diolethoxylates (such as those described in U.S. Pat. No. 6,717,019, whichis herein incorporated by reference). Examples of commercial defoamingsurfactants include Surfynol 440, Surfynol 104, Surfynol MD-20, TroysolS366, Coastal 1017F, Aldo LF, Dow DB-100, and Dow DSP. In someembodiments, defoaming surfactants are Surfynol MD-20, Surfynol 104, andTroysol S366. In some embodiments, the compositions of the disclosure donot contain a defoaming surfactant.

In some embodiments, the stripping compositions of this disclosurecontain the at least one defoaming surfactant in an amount of at leastabout 0.01% by weight (e.g., at least about 0.03% by weight, at leastabout 0.05% by weight or at least about 0.1% by weight) and/or at mostabout 3% by weight (e.g., at most about 2% by weight, at most about 1%by weight or at most about 0.5% by weight).

In addition, in some embodiments, the stripping compositions of thepresent disclosure can contain additional additives such as, pHadjusting agents (such as organic acids, inorganic acids, and organicbases), corrosion inhibitors, chelating agents, surfactants, organicsolvents (e.g., glycol diethers), and biocides, as optional components.

In some embodiments, the stripping compositions of the presentdisclosure may specifically exclude one or more of the followingcomponents, in any combination, if more than one. Such components areselected from the group consisting of oxygen scavengers, amidoximes,oxidizing agents (e.g., peroxides, oxoammonium compounds, inorganicoxidizing agents, and peracids), abrasives (e.g., silica or alumina),fluoride containing compounds, alkali metal and alkaline earth bases(such as NaOH, KOH, magnesium hydroxide, calcium hydroxide and LiOH),metal halide compounds, phosphinic acids, tetrahydrofurfuryl alcohol,glycols, furanyl alcohol, glycerine, saccharides, aryl ethers, N-hydroxyformamide, alkanolamines, N-alkylalkanolamines, sulfonated polymers,metal sulfonates, hydroxylamine, 2-aminobenzothiazole,thiobenzotriazole, sulfonated polyesters, urea compounds, silicatebases, silanes, silicon compounds, surfactants other than a defoamingsurfactant, pyrolidone, steric hindered amide solvents such as1,3-dimethyl-2-piperidone and 1,5-dimethyl-2-piperidone, sulfurcompounds other than DMSO or dimethylsulfone or triazole compoundscontaining sulfur containing substituents, tetrazolium salts, boric acidand derivatives of boric acid, benzimidazoles, non-triazole containingphenolic compounds, chelating agents, and corrosion inhibitors otherthan the Cu or Al corrosion inhibitors described in this disclosure.

In some embodiments, the stripping compositions of this disclosurecontain, consist of, or consist essentially of at least about 30% byweight (e.g., at least about 40% by weight, at least about 50% by weightor at least about 60% by weight) and/or at most about 90% by weight(e.g., at most about 85% by weight, at most about 80% by weight or atmost about 75% by weight) of at least one water soluble polar aproticsolvent; optionally, at least about 5% by weight (e.g., at least about7% by weight, at least about 10% by weight or at least about 12% byweight) and/or at most about 60% by weight (e.g., at most about 45% byweight, at most about 35% by weight or at most about 25% by weight) ofat least one alcohol solvent; at least about 0.1° A by weight (e.g., atleast about 0.5% by weight, at least about 1% by weight or at leastabout 1.5% by weight) and/or at most about 10% by weight (e.g., at mostabout 8% by weight, at most about 5% by weight or at most about 3% byweight) of at least one quaternary ammonium hydroxide; at least about2.5% by weight (e.g., at least about 5% by weight, at least about 7% byweight or at least about 10% by weight) and/or at most about 25% byweight (e.g., at most about 20% by weight, at most about 15% by weightor at most about 12.5% by weight) of water; at least about 0.01% byweight (e.g., at least about 0.05% by weight, at least about 0.1% byweight or at least about 0.5% by weight) and/or at most about 10% byweight (e.g., at most about 7% by weight, at most about 5% by weight orat most about 2% by weight) of at least one copper corrosion inhibitorselected from 6-substituted 2,4-diamino-1,3,5-triazines; optionally, atleast about 0.01% by weight (e.g., at least about 0.03% by weight, atleast about 0.05% by weight or at least about 0.1% by weight) and/or atmost about 3% by weight (e.g., at most about 2% by weight, at most about1% by weight or at most about 0.5% by weight) of at least one defoamingsurfactant; at least about 5 ppm (e.g., at least about 7 ppm, at leastabout 8 ppm, or at least about 10 ppm) and/or at most about 40 ppm(e.g., at most about 35 ppm, at most about 25 ppm, at most about 20 ppm,or at most about 15 ppm) of at least one Group II metal cation; at leastabout 0.1% by weight (e.g., at least about 0.5% by weight, at leastabout 1% by weight or at least about 1.5% by weight) and/or at mostabout 10% by weight (e.g., at most about 8% by weight, at most about 5%by weight or at most about 3% by weight) of at least one compound havingat least three hydroxyl groups; at least about 0.1% by weight (e.g., atleast about 0.2% by weight, at least about 0.3% by weight or at leastabout 0.4% by weight) and/or at most about 1.5% by weight (e.g., at mostabout 1.2% by weight, at most about 0.9% by weight or at most about 0.6%by weight) of at least one carboxylic acid.

The stripping compositions of the present disclosure generally arealkaline in nature. In some embodiments, the stripping compositions ofthe present disclosure has a pH of at least about 13 (e.g., at leastabout 13.5 or at least about 14). Without wishing to be bound by theory,it is believed that the alkaline nature of the stripping compositionscan facilitate removal of a photoresist on a semiconductor substrate.

One embodiment of the present disclosure is a method of stripping orremoving photoresist from a semiconductor substrate. The method includescontacting a semiconductor substrate containing a photoresist or aphotoresist residue with a stripping composition described herein for atime and at a temperature sufficient to remove the photoresist resist orphotoresist residue from the substrate surface. The method can furtherinclude rinsing the semiconductor substrate with a rinse solvent afterthe contacting step and/or drying the semiconductor substrate after therinsing step. In some embodiments, the method does not substantiallyremove Cu or Al in the semiconductor substrate.

In some embodiments, the photoresist stripping methods include the stepsof:

-   -   (A) providing a semiconductor substrate having a photoresist        coating or a photoresist residue;    -   (B) contacting said semiconductor substrate with a stripping        composition described herein to remove the photoresist coating        or the photoresist residue;    -   (C) rinsing said semiconductor substrate with a suitable rinse        solvent; and    -   (D) optionally, drying said semiconductor substrate by any        suitable means that removes the rinse solvent and does not        compromise the integrity of said semiconductor substrate. In        some embodiments, the stripping method further includes forming        a semiconductor device (e.g., an integrated circuit device such        as a semiconductor chip) from the semiconductor substrate        obtained by the method described above.

The semiconductor substrates to be stripped in this method have at leastone photoresist (e.g., a positive or negative photoresist) that needs tobe removed. Semiconductor substrates typically are constructed ofsilicon, silicon germanium, Group III-V compounds like GaAs, or anycombination thereof. The semiconductor substrates may additionallycontain exposed integrated circuit structures such as interconnectfeatures like metal lines and dielectric materials. Metals and metalalloys used for interconnect features include, but are not limited to,aluminum, aluminum alloyed with copper, copper, titanium, tantalum,cobalt, nickel, silicon, polysilicon titanium nitride, tantalum nitride,tin, tungsten, SnAg, SnAg/Ni, CuNiSn, CuCoCu, and CoSn. Saidsemiconductor substrate may also contain layers of interlayerdielectrics, silicon oxide, silicon nitride, silicon carbide, titaniumoxide, and carbon doped silicon oxides.

The semiconductor substrate can be contacted with a strippingcomposition by any suitable method, such as placing the strippingcomposition into a tank and immersing and/or submerging thesemiconductor substrate into the stripping composition, spraying thestripping composition onto the semiconductor substrate, streaming thestripping composition onto the semiconductor substrate, or anycombinations thereof. In some embodiments, the semiconductor substrateis immersed into the stripping composition.

The stripping compositions of the present disclosure can be effectivelyused up to a temperature of about 90° C. In some embodiments, thestripping compositions can be used from about 25° C. to about 80° C. Insome embodiments, the stripping compositions can be employed in thetemperature range from about 30° C. to about 60° C. In some embodimentsthe stripping compositions can be employed in the temperature range ofabout 40° C. to about 60° C. Ultimately for safety reasons, the maximumtemperature is kept significantly below the flash points of the solventsbeing employed.

Similarly, stripping times can vary over a wide range depending on theparticular stripping method, temperature and stripping compositionemployed. When stripping in an immersion batch type process, a suitabletime range is, for example, up to about 60 minutes. In some embodiments,a suitable time range for a batch type process is from about 1 minute toabout 60 minutes. In some embodiments, a suitable time range for a batchtype process is from about 3 minutes to about 20 minutes. In someembodiments, a suitable time range for a batch type stripping process isfrom about 4 minutes to about 15 minutes.

Stripping times for a single wafer process can range from about 10seconds to about 5 minutes. In some embodiments, a stripping time for asingle wafer process can range from about 15 seconds to about 4 minutes.In some embodiments, a stripping time for a single wafer process canrange from about 15 seconds to about 3 minutes. In some embodiments, astripping time for a single wafer process can range from about 20seconds to about 2 minutes. In some embodiments, one or moreapplications of a stripping composition can take place. The volume of astripping composition employed in single wafer process is typicallysufficient to fully cover the substrate, which will depend on thesubstrate size and the surface tension of the stripping composition.

To further promote the stripping ability of the stripping compositionsof the present disclosure, mechanical agitation means can be employed.Examples of suitable agitation means include circulation of a strippingcomposition over the substrate, streaming or spraying a strippingcomposition over the substrate, and ultrasonic or megasonic agitationduring the stripping process. The orientation of the semiconductorsubstrate relative to the ground can be at any angle. In someembodiments, horizontal or vertical orientations are suitable.

The stripping compositions of the present disclosure can be used instripping tools known to those skilled in the art. A significantadvantage of the stripping compositions of the present disclosure isthat they include relatively non-toxic, non-corrosive, and non-reactivecomponents in whole and in part, whereby the compositions are stable ina wide range of temperatures and process times. The strippingcompositions of the present disclosure are generally chemicallycompatible with practically all materials used to construct existing andproposed semiconductor wafer stripping process tools for batch andsingle wafer stripping.

Subsequent to the stripping, the semiconductor substrate is rinsed witha suitable rinse solvent for about 5 seconds up to about 5 minutes withor without agitation means. Examples of suitable rinse solvents include,but are not limited to, deionized (DI) water, methanol, ethanol,isopropyl alcohol, N-methylpyrrolidinone, gamma-butyrolactone, dimethylsulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate.In some embodiments, examples of rinse solvents include, but are notlimited to, DI water, methanol, ethanol and isopropyl alcohol. In someembodiments, rinse solvents are DI water and isopropyl alcohol. In someembodiments, the rinse solvent is DI water. The solvent can be appliedusing means similar to that used in applying a stripping compositiondescribed herein. The stripping composition may have been removed fromthe semiconductor substrate prior to the start of the rinsing step or itmay still be in contact with the semiconductor substrate at the start ofthe rinsing step. In some embodiments, the temperature employed in therinsing step is between 16° C. and 27° C.

Optionally, the semiconductor substrate is dried after the rinsing step.Any suitable drying means known in the art can be employed. Examples ofsuitable drying means include spin drying, flowing a dry gas across thesemiconductor substrate, or heating the semiconductor substrate with aheating means such as a hotplate or infrared lamp, Maragoni drying,rotagoni drying, IPA drying or any combinations thereof. Drying timeswill be dependent on the specific method employed but are typically onthe order of 30 seconds up to several minutes.

In some embodiments, the semiconductor substrate can subsequently beprocessed to form one or more additional circuits on the substrate orcan be processed to form into a semiconductor chip by, for example,assembling (e.g., dicing and bonding) and packaging (e.g., chipsealing).

The present disclosure is illustrated in more detail with reference tothe following examples, which are for illustrative purposes and shouldnot be construed as limiting the scope of the present disclosure.

EXAMPLES

General Procedure 1 (Stripper Formulation)

Stripping compositions were prepared by mixing, while stirring, theorganic solvents, and ultra-pure deionized water (DIW). Aqueous (25%)TMAH was added slowly while stirring, followed by the Cu inhibitor.After a uniform solution was achieved, the remaining components wereadded, followed by the optional components, if used. All components usedwere commercially available and of high purity.

pH measurements, if desired, were taken at ambient temperature (17-25°C.) after all components were fully dissolved. Beckman Coulter ϕ400Series Handheld meters can be used for these pH measurements.

General Procedure 2 (Stripping Tests)

Stripping tests were conducted using customer provided full 200 mm or300 mm wafers. The customer-provided wafers with thick positive ornegative-tone resists were diced into small coupons containing integraldies for the stripping tests. The samples were placed in a 600 mL volumeglass beaker containing approximately 200 mL of the strippingcompositions of the present disclosure. Prior to immersion of a sampleinto a stripping composition, the stripping composition was pre-heatedto the test condition temperature (typically 50° C. to 80° C.) on ahotplate set at approximately 250 rpm for controlled solution agitation.The stripping tests were then carried out by placing the sample into theheated stripping composition with device side “face to” the stir bar andleaving the sample in the solution with constant agitation for the testcondition time (typically 0.5 to 10 minutes). Once the sample wasexposed in the solution for the duration of the test condition, thesample was quickly removed from the test solution with a pair of plastic“locking” tweezers, and placed in a 600 mL plastic beaker filled withapproximately 500 mL of ultra-pure deionized water at ambienttemperature (˜17° C.). The sample was left in the beaker of deionizedwater for approximately 10-20 seconds with mild agitation, and thenremoved and placed under an ultra-pure de-ionized water stream (flowrate ˜2 L/min) at ambient temperature for an additional 40-50 seconds,and then removed. Upon removal, the sample was immediately exposed tonitrogen gas from a hand held nitrogen blowing gun which caused anydroplets on the sample surface to be blown off the sample, and furtherto completely dry the sample device surface and backside. Following thisfinal nitrogen drying step, the sample was removed from the plastictweezers holder and placed into a covered plastic carrier with thedevice side up for short term storage no greater than about 2 hours.Scanning electron microscopy (SEM) images were then collected for keyfeatures (i.e. SnAg/Ni bumps) on the stripped test sample devicesurface.

General Procedure 3 (Etch Rate Measurements)

Etch rates of various substrate materials were measured to determine thecorrosivity of tested stripping compositions. Coupons (Cu, Al, W, Ni,Sn, Co, silicon nitride, or poly-Si) from wafers having a coating of thephotoresist material being tested were immersed in a certain volume of atest stripping composition pre-heated to the test condition temperature.After immersion in the test stripping composition for the duration ofthe test condition time, the coupons were quickly removed from the testcomposition with a pair of plastic “locking” tweezers, rinsed bydeionized water, blow dried by N₂ gas flow.

The thickness of dielectric films on the coupons before and afterdipping in the test composition was measured by either an Ellipsometeror Filmetrics film thickness measuring devices. The difference in filmthickness divided by the etch time was used to calculate the etch rate.

The sheet resistance of the metal film on the coupons before and afterdipping in the test composition was measured by a Resmap 4-point probeinstrument. On metals except Sn, a correlation between film thicknessand sheet resistance was employed to determine film thickness. The etchrate was determined by dividing the film thickness change by theimmersion time in the composition.

Comparative Example 1 (CE-1) and Formulation Examples 1-3 (FE-1 toFE-33)

The data in Table 1 illustrate two aspects of the effect of the sugaralcohol glycerol on formulations of the disclosure. First, compared toCE-1 (with no glycerol), FE-1 to FE-3 demonstrate that glycerol aids inthe dissolution of Ca into the alkaline semi-aqueous formulations. Clearformulations result when glycerol is included in the formulations,whereas undissolved white powder is observed in CE-1. Second, improvedAl etch resistance is observed (i.e., decreased Al etch rates) as theglycerol concentration increases.

TABLE 1 Wt % Except Ca (Ca conc. given in PPM) CE-1 FE-1 FE-2 FE-3 Ca 30ppm 30 ppm 30 ppm 30 ppm DMSO 71.54 70.89 70.24 68.38 MMB 11.11 11.0010.90 10.62 TMAH 2.31 2.29 2.27 2.21 Benzoguanamine 0.46 0.46 0.45 0.44MD-20 0.19 0.18 0.18 0.18 Citric acid 0.46 0.46 0.45 0.44 Glycerol 0.000.92 1.82 4.42 DIW 13.88 13.76 13.63 13.27 Ca citrate 0.041 0.040 0.0400.039 tetrahydrate Look after 1 h White powder Clear Clear Clearstirring @RT Al ER 4.2 2.1 −0.9 0.9 (70 C./10 min.) Cu ER 2.4 2.2 1.61.1 (70 C./10 min.) TSV 100% clean 100% clean 100% clean 90% (70 C./2min.) clean CuNiSn bump 95% clean 100% clean 100% clean 95% (70 C./2min.) clean DMSO = dimethylsulfoxide MMB = 3-methoxy-3-methyl-butanolTMAH = tetramethylammonium hydroxide MD-20 = acetylenic surfactant DIW =de-ionized water TSV = through silicon vias

Formulation Examples 4-8 (FE-4 to FE-8) and Comparative Examples 2 and 3(CE-2 and CE-3)

TABLE 2 Wt % Except Ca (Ca conc. given in PPM) FE-4 FE-5 FE-6 FE-7 FE-8CE-2 CE-3 Ca 12 ppm 27 ppm 27 ppm 27 ppm 27 ppm 0 ppm 0 ppm DMSO 79.3678.32 76.98 75.68 74.43 76.99 75.69 TMAH 2.20 3.05 2.99 2.94 2.89 2.992.94 Benzoguanamine 0.44 0.44 0.43 0.42 0.41 0.43 0.42 Citric acid 0.350.35 0.34 0.34 0.33 0.34 0.34 Glycerol 4.41 4.35 5.99 7.57 9.10 5.997.57 DIW 13.23 13.49 13.26 13.03 12.82 13.26 13.04 Ca citrate 0.0070.013 0.013 0.013 0.012 0.000 0.000 tetrahydrate Look after 20 h ClearClear Clear Clear Clear Clear Clear stirring @RT Al ER (A/min., 11.2 0.62.0 −0.1 0.1 40.8 33.5 70 C./10 min.) 10/1 TSV, 100% 100% 100% 100% 100%100% 100% (70 C./2 min.) clean Clean Clean Clean Clean Clean CleanCuNiSn bump 100% 100% 95% 100% 100% 100% 100% (70 C./2 min.) clean Cleanclean Clean Clean Clean Clean

The data in Table 2 demonstrate that formulations containing Group IImetal ions were able to suppress Al etch rates as compared toformulations without a Group II metal ion. In these examples, the effectis demonstrated using Ca²⁺ as an exemplary Group II metal ion.

Formulation Examples 9-11 (FE-9 to FE-11) and Comparative Example 4(CE-4)

TABLE 3 Wt % except Ca (Ca conc. given in PPM) FE-9 FE-10 CE-4 FE-11DMSO 72.6% 72.6% 73.0% 68.4% MMB 11.3% 11.3% 11.3% 11.3% TMAH  2.3% 2.3%  2.3%  2.3% Benzoguanamine 0.47% 0.47% 0.47% 0.47% MD20 0.19%0.19% 0.19% 0.19% Citric acid 0.47% 0.47%   0% 0.47% Glycerol 0.94%0.94% 0.94% 2.82% DIW 11.7% 11.7% 11.7% 14.1% Calcium chloride 0.0080%   0%   0%   0% Calcium Citrate   0% 0.0408%  0.0408%  0.0408% Tetrahydrate Total 100.0%  100.000%   100.000%   100.0%  Ca Load 30 ppm30 ppm 30 ppm 30 ppm Look @70 C. Clear Clear solids in solution Clearafter 24 hr stir Al ER (70 C./10 min.) 11.4 −1.8 208 −1 imec Cu ER −2.2−2.4 0 3.2 (70 C./5 min.) TSV (70 C./2 min.)  100%  100%  100%  100% Cubump (70 C./2 min.)  100%  100%  100%  100%

The data in Table 3 demonstrate that carboxylic acids facilitatedsolubilizing the Group II metal ion in the organic solvent basedformulations of the disclosure. Without wishing to be bound by theory,it is believed that chelating carboxylic acids (such as citric acid) actin concert with sugar alcohols (such as glycerol) to solubilize theGroup II metal ion (e.g., Ca²⁺ in FE-9 to FE-11). Specifically, theresults show that formulations FE-9 to FE-11 (which included both citricacid and glycerol) exhibited low Al etch rates. For comparative example4 (i.e., formulation CE-4 containing glycerol but no citric acid),solids were present in the formulation even after a 24 hour stir, andthe Al etch rate for formulation CE-4 was unacceptably high.

In addition, the data in Table 3 demonstrate that the Group II metal ioncan be introduced to the formulation by using different Group II metalsalts (e.g., calcium chloride, calcium citrate, and the like).

Formulation Examples 12-16 (FE-12 to FE-16)

TABLE 4 Wt % except Ca or Sr (Ca or Sr conc. given in PPM) FE-12 FE-13FE-14 FE-15 FE-16 Citric acid 0.34% 0.34% 0.68% 0.34% 0.34% Glycerol7.24%   0% 7.24% 7.24% 7.24% Sorbitol   0% 5.11%   0%   0%   0% DIW12.8% 12.8% 12.8% 12.8% 12.8% Ca citrate 0.0106%  0.0106%  0.0106%    0%  0% tetrahydrate Strontium Acetate   0%   0%   0% 0.0054%  0.0324% DMSO 77.1% 79.2% 76.7% 77.1% 77.1% TMAH 2.13% 2.13% 2.13% 2.13% 2.13%Benzoguanamine 0.43% 0.43% 0.43% 0.43% 0.43% Ca or Sr 22 ppm 22 ppm 22ppm 22 ppm 134 ppm Look after >24 h Small amount Slightly more SmallPowder No Powder Small stirring @RT Powder Powder Powder 0.2 μmfiltration Yes Yes Yes Yes Yes before beaker test Al ER (A/min., 5.8−0.7 9.6 5.8 −1.9 70 C./10 min.) Cu ER (A/min 70 C. 5 min) −7 4.8 −1.4−2 −1.6

The data in Table 4 demonstrate that Group II metal ions other than Ca²⁺were also able to suppress Al etch rates. Formulation Examples 15 and 16demonstrate effective Al etch inhibition with Sr²⁺. Table 4 alsoillustrates the effectiveness of the sugar alcohol sorbitol insolubilizing the Group II metal ion.

Formulation Examples 17-21 (FE-17 to FE-21)

TABLE 5 Wt % except Ca FE-17 FE-18 FE-19 FE-20 FE-21 Ca 18 ppm 22 ppm 27ppm 22 ppm 22 ppm DMSO 76.65 76.65 76.65 76.33 75.69 TMAH 2.13 2.13 2.132.54 2.94 Benzoguanamine 0.43 0.43 0.43 0.42 0.42 Citric acid 0.34 0.340.34 0.34 0.34 Glycerol 7.67 7.67 7.67 7.63 7.57 DIW 12.78 12.78 12.7812.72 13.03 Ca citrate 0.009 0.011 0.013 0.011 0.011 tetrahydrateSolution after 19 h Clear Clear Clear Clear Clear stirring @RT Solutionafter 40 h Clear Clear Clear Clear Clear stirring @RT 0.2um filtrationDone Done Done Done Done before beaker test Al ER (A/min., 2.3 1.5 −2.31.0 −2.5 70 C./10 min.) Cu ER (A/min., 0.7 0.7 1.3 1.2 1.3 70 C./10min.) 10/1 TSV, Clean Clean Clean Clean Clean (70 C./2 min.) CuNiSn bumpClean Clean Clean Clean Clean (70 C./2 min.)

The data in Table 5 further demonstrate the effectiveness offormulations of the disclosure in removing photoresist from TSV's andmicro-bump structures, while maintaining excellent Al and Cucompatibility.

Formulation Examples 22 to 43

To further elaborate on the compositions of this disclosure, additionalformulations are described in Table 6.

TABLE 6 Formulation Quat. Multi-hydroxy Group II Example CarboxylicHydroxide H₂O Cu Etch compound metal ion Number Solvent (%) acid (%) (%)(%) Inhibitor (%) (%) (M²⁺, ppm) FE-22 NMP (89.8) Citric tetramethyl 7.56-methyl- Glycerol Mg (0.1) ammonium 1,3,5-triazine- (0.1) (18)hydroxide 2,4-diamine (2) (0.5) FE-23 NMP (88.8) Maleic choline 7.51,3,5- Sorbitol Ca (0.2) (2.5) Triazine-2,4- (0.5) (21) diamine, 6-[2-(2- furanyl)ethyl]- (0.5) FE-24 DMSO (89.9) Fumaric tetraethyl- 6.3Benzo- Mannitol Sr (0.3) ammonium guanamine (1.0) (24) hydroxide (0.5)(2) FE-25 DMSO (71.6) Lactic tetramethyl 25 Benzo- Erythritol Ba (0.4)ammonium guanamine (2.0) (27) hydroxide (0.5) (0.5) FE-26 DMSO (87.5)Glycolic benzyl- 2.5 6-methyl- Arabitol Mg (0.5) trimethyl-1,3,5-triazine- (3.0) (30) ammonium 2,4-diamine hydroxide (5) (1.5)FE-27 NMP (74.4) Oxalic tetramethyl 15 1,3,5- Isomalt Ca (0.6) ammoniumTriazine-2- (4.0) (10) hydroxide propanoic (5) acid, 4,6- diamino-, (1)FE-28 Sulfolane Tartaric tetramethyl 15 Benzo- Lactitol Sr (75.8) (0.7)ammonium guanamine (5.0) (15) hydroxide (1) (2.5)/ benzyl- trimethyl-ammonium hydroxide (2.5) FE-29 Sulfolane Succinic tetramethyl 13 Benzo-Maltitol Ba (76.7) (0.8) ammonium guanamine (6.0) (20) hydroxide (1)/6-(3) methyl-1,3,5- triazine-2,4- diamine (0.5) FE-30 DMSO (78.4) Benzoictetramethyl 10 6-methyl- Xylitol Mg (0.9) ammonium 1,3,5-triazine- (7.0)(25) hydroxide 2,4-diamine (3) (0.7) FE-31 1,3-dimethyl- Citric benzyl-12 6-methyl- Threitol Ca 2- (1.0) trimethyl- 1,3,5-triazine- (8.0) (30)imidazolidinone ammonium 2,4-diamine (64) hydroxide (5) (10) FE-32dimethyl Maleic tetramethyl 20 6- Ribitol Sr sulfone (63.1) (1.1)ammonium [(phenylthio)methyl]-, (9.0) (35) hydroxide 1,3,5- (5.8)Triazine-2,4- diamine (1) FE-33 DMSO (74.3) Fumaric tetramethyl 10Benzo- Galactitol Ba (1.2) ammonium guanamine (10.0) (40) hydroxide(0.5) (4) FE-34 NMP (80.1) Lactic choline 14 6-methyl- Iditol Mg (1.3)(3.5) 1,3,5-triazine- (0.1) (12) 2,4-diamine (1) FE-35 DMSO (75.1)Glycolic tetramethyl 15 Benzo- Inositol Ca (1.4) ammonium guanamine(0.5) (15) hydroxide (3) (5) FE-36 DMSO (84) Oxalic tetramethyl 126-methyl- Glycerol Sr (1.5) ammonium 1,3,5-triazine- (1.0) (18)hydroxide 2,4-diamine (0.5) (1) FE-37 DMSO (76.6) Tartaric tetraethyl-18 Benzo- Sorbitol Ba (0.1) ammonium guanamine (2.0) (21) hydroxide(1.3) (2) FE-38 1,3-dimethyl- Succinic benzyl- 20 6-methyl- Mannitol Mg2- (0.2) trimethyl- 1,3,5-triazine- (3.0) (24) imidazolidinone ammonium2,4-diamine (61.8) hydroxide (5) (10) FE-39 Sulfolane Benzoictetramethyl 16 Benzo- Lactitol Ca (76.2) (0.3) ammonium guanamine (4.0)(27) hydroxide (1) (2.5)/ benzyl- trimethyl- ammonium hydroxide (2.5)FE-40 dimethyl citric tetramethyl 20 6- Arabitol Sr sulfone (0.4)ammonium [(phenylthio)methyl]-, (5.0) (30) (67.8) hydroxide 1,3,5- (5.8)Triazine-2,4- diamine (1) FE-41 DMSO (73) Maleic tetramethyl 15 Benzo-Threitol Ba (0.5) ammonium guanamine (6.0) (33) hydroxide (0.5)/6- (5)methyl-1,3,5- triazine-2,4- diamine (0.5) FE-42 dimethyl Fumaric choline10 6-methyl- Isomalt Mg sulfone (0.6) (0.1) 1,3,5-triazine- (7.0) (36)(72.3) 2,4-diamine (10) FE-43 NMP Lactic tetramethyl 7.3 6-methyl-Ribitol Ca (81.5) (0.7) ammonium 1,3,5-triazine- (8.0) (39) hydroxide2,4- (2) diamine (0.5)

While the disclosure has been described in detail with reference tocertain embodiments thereof, it is understood that modifications andvariations are within the spirit and scope of that which is describedand claimed.

What is claimed is:
 1. A composition, comprising: 1) at least one watersoluble polar aprotic organic solvent; 2) at least one quaternaryammonium hydroxide; 3) at least one compound comprising at least threehydroxyl groups; 4) at least one carboxylic acid; 5) at least one GroupII metal cation; 6) at least one copper corrosion inhibitor selectedfrom the group consisting of 6-substituted-2,4-diamino-1,3,5-triazines;and 7) water.
 2. The composition of claim 1, wherein the at least onequaternary ammonium hydroxide comprises a compound of the formula[NR₁R₂R₃R₄]⁺OH, in which each of R₁, R₂, R₃, and R₄, independently, is alinear, branched, or cyclic alkyl group optionally substituted byhydroxy, a substituted or unsubstituted phenyl group, or a substitutedor unsubstituted benzyl group.
 3. The composition of claim 2, whereineach of R₁, R₂, R₃, and R₄, independently, is a C₁-C₄ alkyl group, ahydroxyethyl group, a phenyl group, or a benzyl group.
 4. Thecomposition of claim 1, wherein the composition comprises the at leastone quaternary ammonium hydroxide in an amount from about 0.1 wt % toabout 10 wt %.
 5. The composition of claim 1, wherein the at least onecopper corrosion inhibitor comprises a6-substituted-2,4-diamino-1,3,5-triazine, the substituent at the6-position being a linear or branched, substituted or unsubstitutedC₁-C₁₂ alkyl group, a substituted or unsubstituted C₃-C₁₂ cycloalkylgroup, a substituted or unsubstituted aryl group, —SCH₂R¹⁰⁰,—N(R¹⁰⁰R¹⁰¹), or imidyl, in which each of R¹⁰⁰ and R¹⁰¹, independently,is a linear or branched, substituted or unsubstituted C₁-C₁₂ alkyl groupoptionally containing a nitrogen or oxygen atom in the alkyl chain, asubstituted or unsubstituted C₃-C₁₂ cycloalkyl group optionallycontaining a nitrogen or oxygen atom in the cycloalkyl ring, asubstituted or unsubstituted aryl group, or R¹⁰⁰ and R¹⁰¹, together withthe atom to which they are attached, form a ring.
 6. The composition ofclaim 1, wherein the at least one copper corrosion inhibitor comprises6-phenyl-2,4-diamino-1,3,5-triazine or6-methyl-2,4-diamino-1,3,5-triazine.
 7. The composition of claim 1,wherein the composition comprises the at least one copper corrosioninhibitor in an amount from about 0.1 wt % to about 10 wt %.
 8. Thecomposition of claim 1, wherein the at least one water soluble polaraprotic organic solvent comprises dimethyl sulfoxide, sulfolane,dimethylsulfone, N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone, gamma-butyrolactone, propylene carbonate,1,3-dimethyl-2-imidazolidinone, or a mixture thereof.
 9. The compositionof claim 1, wherein the composition comprises the at least one watersoluble polar aprotic organic solvent in an amount from about 30 wt % toabout 90 wt %.
 10. The composition of claim 1, further comprising atleast one alcohol solvent.
 11. The composition of claim 10, wherein theat least one alcohol solvent comprises an alkane diol, a glycol, analkoxyalcohol, a saturated aliphatic monohydric alcohol, an unsaturatednon-aromatic monohydric alcohol, an alcohol containing a ring structure,or a mixture thereof.
 12. The composition of claim 10, wherein thecomposition comprises the at least one alcohol solvent in an amount fromabout 5 wt % to about 60 wt %.
 13. The composition of claim 1, whereinthe composition comprises the water in an amount from about 2.5 wt % toabout 25 wt %.
 14. The composition of claim 1, further comprising atleast one defoaming surfactant.
 15. The composition of claim 14, whereinthe composition comprises the at least one defoaming surfactant in anamount from about 0.01 wt % to about 3 wt %.
 16. The composition ofclaim 1, wherein the at least one compound comprising at least threehydroxyl groups comprises a sugar alcohol.
 17. The composition of claim16, wherein the sugar alcohol is glycerol, sorbitol, mannitol,erythritol, arabitol, isomalt, lactitol, maltitol, xylitol, threitol,ribitol, galactitol, iditol, or inositol.
 18. The composition of claim16 wherein the sugar alcohol is glycerol or sorbitol.
 19. Thecomposition of claim 16, wherein the composition comprises the at leastone compound comprising at least three hydroxyl groups in an amount fromabout 0.1 wt % to about 10 wt %.
 20. The composition of claim 1, whereinthe at least one carboxylic acid is selected from the group consistingof monocarboxylic acids, bicarboxylic acids, tricarboxylic acids,α-hydroxyacids and β-hydroxyacids of monocarboxylic acids,α-hydroxyacids and β-hydroxyacids of bicarboxylic acids, andα-hydroxyacids and β-hydroxyacids of tricarboxylic acids.
 21. Thecomposition of claim 20, wherein the at least one carboxylic acidcomprises citric acid, maleic acid, fumaric acid, lactic acid, glycolicacid, oxalic acid, tartaric acid, succinic acid, or benzoic acid. 22.The composition of claim 21, wherein the at least one carboxylic acidcomprises citric acid.
 23. The composition of claim 1, wherein thecomposition comprises the at least one carboxylic acid in an amount fromabout 0.1 wt % to about 1.5 wt %.
 24. The composition of claim 1,wherein the at least one Group II metal cation comprises Mg²⁺, Ca²⁺,Sr²⁺, or Ba²⁺.
 25. The composition of claim 1, wherein the at least oneGroup II metal cation comprises Ca²⁺.
 26. The composition of claim 1,wherein the composition comprises the at least one Group II metal cationin an amount from about 5 ppm to about 40 ppm.
 27. The composition ofclaim 1, wherein the composition has a pH of at least about
 13. 28. Amethod, comprising: contacting a semiconductor substrate containing aphotoresist or a photoresist residue with the composition of claim 1 toremove the photoresist or photoresist residue.
 29. The method of claim28, further comprising rinsing the semiconductor substrate with a rinsesolvent after the contacting step.
 30. The method of claim 29, furthercomprising drying the semiconductor substrate after the rinsing step.31. The method of claim 28, wherein the method does not substantiallyremove Cu or Al in the semiconductor substrate.